1-(4-bromophenyl)-2,2,4,4,4-pentafluoro-3,3-dihydroxybutan-1-one | 1616792-34-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(4-bromophenyl)-2,2,4,4,4-pentafluoro-3,3-dihydroxybutan-1-one
• CAS: 1616792-34-7
• 化学式: C₁₀H₆BrF₅O₃
• 分子量: 349.052
• InChiKey: GZYKQKPBUMLWJK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  57.5
• 氢给体数：
  2
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1-(4-bromophenyl)-2,2,4,4,4-pentafluoro-3,3-dihydroxybutan-1-one 在 iron(II) triflate 、 过氧化苯甲酸叔丁酯 、 叠氮基三甲基硅烷 、 碘 、 lithium bromide 作用下， 以 四氢呋喃 、 1,4-二氧六环 为溶剂， 反应 0.5h， 生成 4-azido-1-(4-bromophenyl)-2,2-difluoro-4-phenylbutan-1-one
  参考文献：
  名称：

  Iron‐Catalyzed Intermolecular Azidabenzoyl Difluoromethylation of Alkenes to Access β ‐Difluoroacyl Azides

  摘要：

  AbstractA Fe(II)‐catalyzed three‐component reaction of 2‐iodo‐2,2‐difluoroacetophenones, alkenes and TMSN3 is described, which provides a particularly valuable route to access difluoroalkylated azides with high yields. The method permits the efficient azidation of varied β‐difluoroacyl‐benzylic radicals in mild conditions with high functional group tolerance. Preliminary mechanistic investigation indicated that a radical‐mediated process was involved in this azidadifluoroacylation reaction.

  DOI：

  10.1002/ejoc.202201213
• 作为产物：
  描述：

  1-(4-bromophenyl)-2,2,4,4,4-pentafluorobutane-1,3,3-triol 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以78%的产率得到1-(4-bromophenyl)-2,2,4,4,4-pentafluoro-3,3-dihydroxybutan-1-one
  参考文献：
  名称：

  Generation of Magnesium Pentafluoropropen-2-olate from Hexafluoroisopropanol and Synthesis of 2,2,4,4,4-Pentafluoro-3,3-dihydroxyketones

  摘要：

  2,2,4,4,4-Pentafluoro-3,3-dihydroxyketones are valuable precursors to difluoroenolates following fragmentation during the release of trifluoroacetate; however, there are few synthetic strategies to prepare this unique class of compound. We addressed this issue and report a mild, two-step synthesis of 2,2,4,4,4-pentafluoro-3,3-dihydroxyketones from aldehydes. Specifically, aldehydes are treated with pentafluoropropen-2-olate, generated from a new fragmentation of hexafluoroisopropanol with a mixed Mg/Li amide, to give pentafluoroalcohols. A subsequent oxidation with Dess-Martin periodinane provides the targets in good isolated yields.

  DOI：

  10.1021/acs.joc.6b02863

文献信息

• Copper‐Catalyzed Three‐Component Reactions of 2‐Iodo‐2,2‐difluoroacetophenones, Alkynes, and Trimethylsilyl Cyanide
  作者：Pingjie Wu、Cheng Zheng、Xia Wang、Jingjing Wu、Fanhong Wu

  DOI：10.1002/ejoc.202001650

  日期：2021.3.5

  Cu(I)‐catalyzed three‐component reaction of 2‐iodo‐2,2‐difluoroacetophenones, alkynes, and TMSCN for the synthesis of useful difluoroacyl‐substituted nitriles is described. This method has broad substrate scope and excellent stereoselectivity. Preliminary mechanistic investigation indicated that a radical‐mediated process was involved in this cyanodifluoroalkylation reaction.

  描述了Cu（I）催化的2-碘-2-2,2-二氟苯乙酮，炔烃和TMSCN的三组分反应，用于合成有用的二氟酰基取代的腈。该方法具有广泛的底物范围和优异的立体选择性。初步的机理研究表明，该氰基二氟烷基化反应涉及自由基介导的过程。
• Synthesis of α,α-difluoro-β-amino carbonyl-containing sulfonamides and related compounds
  作者：Chen Xie、Lingmin Wu、Jie Zhou、Haibo Mei、Vadim A. Soloshonok、Jianlin Han、Yi Pan

  DOI：10.1016/j.jfluchem.2015.01.004

  日期：2015.4

  Mannich addition reactions between in situ generated α,α-difluoroenolates and various N-sulfonyl imines readily occur with exceptionally high reaction rates at ambient temperature. The method features remarkable generality and enjoys operationally convenient conditions underscoring its practicality and methodological importance for preparation of sulfonamides bearing β-amino-α,α-difluoro ketone moiety

  在环境温度下，原位生成的α，α-二氟烯酸酯与各种N-磺酰基亚胺之间的曼尼希加成反应很容易发生。该方法具有显着的通用性，并具有操作方便的条件，这突出了其制备具有β-氨基-α，α-二氟酮部分的磺酰胺的实用性和方法学重要性。
• Microwave-Assisted Copper Catalysis of α-Difluorinated <i>gem</i>-Diol toward Difluoroalkyl Radical for Hydrodifluoroalkylation of <i>para</i>-Quinone Methides
  作者：Chuan-Hua Qu、Gui-Ting Song、Dian-Yong Tang、Jing-Wei Shao、Hong-yu Li、Zhi-Gang Xu、Zhong-Zhu Chen

  DOI：10.1021/acs.joc.0c01686

  日期：2020.10.2

  gem-diols by single electron oxidation. Under microwave irradiation, a catalytic amount of oxidant Cu(OAc)2 succeeds in the formation of transient difluoroalkyl radicals in situ, for the first time. The reaction features a simple protocol, short reaction time, scalability, and high yield. The synthetic utility of this new methodology was also explored for the synthesis of difluoroalkylated spiro-cyclohexadienones

  本文报道的是生成从容易地制备α -二氟化的二氟烷基自由基的统一策略宝石由单电子氧化-diols。在微波辐射下，催化量的氧化剂Cu（OAc）2首次成功地在原位形成了瞬态二氟烷基。该反应具有操作简单，反应时间短，可扩展性和高产率的特点。还研究了这种新方法的合成效用，以合成二氟烷基化的螺-环己二酮，这是天然产物和药物中的重要核心结构。
• Synthesis of α,α-difluorobenzoyl oxygen heterocycles via the radical reaction of 2-iodo-2,2-difluoroacetophenones with unsaturated acids or unsaturated alcohols
  作者：Heng Chen、Jiexiong Wang、Jingjing Wu、Yujia Kuang、Fanhong Wu

  DOI：10.1016/j.jfluchem.2017.06.003

  日期：2017.8

  A convenient and facile method for the direct synthesis of α,α-difluorobenzoyl lactones or cyclic ethers via the radical cyclization reaction of 2-iodo-2,2-difluoroacetophenone with unsaturated acids or alcohols was reported.

  据报道，通过2-碘-2，2-二氟苯乙酮与不饱和酸或醇的自由基环化反应，直接合成α，α-二氟苯甲酰基内酯或环醚的简便方法。
• Generalized access to fluorinated β-keto amino compounds through asymmetric additions of α,α-difluoroenolates to CF₃-sulfinylimine
  作者：Chen Xie、Lingmin Wu、Haibo Mei、Vadim A. Soloshonok、Jianlin Han、Yi Pan

  DOI：10.1039/c4ob01575d

  日期：——

  CF3-containing chiral imines readily react with α,α-difluoroenolates affording a novel type of β-keto-amino compounds featuring the R-CO-CF2-CH(NH2)-CF3 moiety. The reactions feature exceptional generality allowing preparation of various aromatic, hetero-aromatic and aliphatic derivatives in high yields and diastereoselectivity. The products are configurationally stable and can be transformed to more

  含CF 3的手性亚胺容易与α，α-二氟烯酸酯反应，得到新型的具有R-CO-CF 2 -CH（NH 2）-CF 3部分的β-酮-氨基化合物。该反应具有出色的通用性，可以高产率和非对映选择性地制备各种芳族，杂芳族和脂族衍生物。产品在结构上是稳定的，可以转化为官能度更高的复杂化合物。